Our research demonstrates electrospun nonwoven fibrous scaffolds from a low molar mass gemini ammonium surfactant, N,N'-didodecyl-N,N',N',N'-tetramethyl-N,N'-ethanediyldiammonium dibromide (12-2-12). Cryogenic transmission electron microscopy (cryo-TEM) and solution rheological experiments revealed micellar morphological transitions of 12-2-12 in water and wate:methanol (1:1 vol). The microstructure of 12-2-12 in water transitioned from entangled, cylindrical, threadlike micelles to branched threadlike micelles, and a viscoelastic, entangled, highly branched network of threadlike micelles with increasing concentration finally formed. In sharp contrast, the solution behavior of 12-2-12 in water:methanol produced a drastically different micellar microstructure compared to that in water, and the morphology transitioned from partitioned, globular micelles to overlapped micelles at an overlap concentration (C*) of 11 wt%. Electrospinning 12-2-12 from water did not produce fibers at any concentration; however, electrospinning 12-2-12 in water:methanol at concentrations greater than 2C* produced hydrophilic continuous fibers with diameters ranging from 0.9 to 7 mu m. High surface area scaffolds with hydrophilic surfaces offer potential as charged controlled-release membranes, tissue engineering scaffolds, and coatings for biologically compatible devices.